Macrocyclic hetero imine complexing agents

ABSTRACT

1. 5,6,14,15 - DIBENZO - 4,7,13,16 - TETRAOXA - 1,10 - DIAZACYCLOOCTADECA-5,14-DIENE.

United States a ABSTRACT OF THE DISCLOSURE- x Macrocyclic imines usefulas complexing agents for ionic metal compounds characterized by amacrocyclic ring or rings of carbon and hetero-atoms totaling 14-60 ringatoms, at least one hetero-atom being nitrogen and the remainder beingoxygen, each hetero-atom in the ring being separated from adjoininghetero-atoms by links of 2 or 3 carbon atoms. The macrocyclic ring orrings are fused to 1-4 carbocyclicrings. The macrocyclic rings orsubstituted derivatives of them .canbe monocyclic, bicyclic, or bridgedby a carbon, or carbon-hetero-atom chain.

This invention relates to macrocyclic 'ringcompounds containing carbonand hetero-atoms, such as nitrogen and oxygen.

Macrocyclic compounds containing 14 to about 28 ring atoms selected fromcarbon, sulfur, and oxygen atoms are known. They are known to be usefulfor forming complexing compounds containing certain metal ions wherebyreactions with these compounds can take place in media not otherwiseuseful for this purpose'The complexing ability of macrocyclic compoundsis not uniform with all metal ions but is selective and, therefore, notpredictable with certainty prior to actual testing. Therefore,solubility, complexing ability, and macrocyclic ring configuration ofknown macrocyclic complex forming compounds limit their utility.

According to this invention, there are provided certain macrocyclicimines characterized by at least one macrocyclic ring of carbon andhetero-atomstotaling 14-60.

C -C alkenyl, -0 aryl, (D -C aralkyl, c -C 'cycloalkyl, C -C alkoxy,alkaryl, aeyl, cyano, nitro, nitroso,

carboxy, sulfo, etc.

Molecular models of the representative compounds of the presentinvention has configurations suggestive of .a crown, lantern, or clam.Accordingly herein, the

mono macrocyclic imines are denoted crown compounds, the bicyclicmacrocyclic imines are denoted lantern compounds, and the bridgedmacrocyclic imines are denoted clam compounds. Complexes of thesecompounds with ionic metals are denoted crown, lantern, or clamcomplexes. The crown, lantern, and clam compounds of this invention willbe referred to herein collectively as crown compounds. Basically themacrocyclic imines have the structure 3,847,949 Patented Nov. 12, 1974CCv where W is a hetero atom or group which is in this invention isindependently an imino group (e.g.

or an oxygen atom with at least one nitrogen atom being present in themacrocyclic ring; R is an alkylene group, i.e. '-CH CH or --CH CH CH xis an integer of at least 1; a and b are independently O or a positiveinteger;

is a carbocyclic ring such as phenylene, naphthalene, phenanthralene,anthralene, etc., or saturated analogs thereof, such as cyclohexylene,etc.; and C and C are vicinal carbon atoms in the carbocyclic ring(herein called a fused carbocyclic ring). In other words, the crowncompounds of this invention contain a macrocyclic ring fused to 14 otheraromatic or alicyclic rings (fused rings). The fused rings can be thesame or ditferent and can be arylene (e.g. phenylene) or perhydro (fullysaturated) analogs thereof (e.g. cyclohexylene) or substitutedderivatives of these, the substituents being one or more or acombination of the groups: halo, nitro, amino, azo, alkyl, aryl,aralkyl, aeyl, alkoxy, cyano, hydroxy, carboxy, chlorocarbonyl,carbalkoxy, and sulfo, or any other substituents available through theknown reactions of organic chemistry. Such groups provide a crowncompound with additional functionality and the attendant reactivity andusefulness without detracting from its utility as a complexing agent.

At least two methods are available for synthesizing these substitutedcrown compounds in which one or more substituents are attached to one ormore fused rings. In one method the substituents are present on anaromatic or alicyclic compound which will serve as the starting pointfor making a crown. In this case, these substituent groups must, ingeneral, be reasonably stable toward the reactants needed to promote thedesired ring-closure reaction. In other words, it should be recognizedthat substituents groups can be reactive and require appropriateprotection during the synthesis according to well-known chemicalprinciples. Standard methods for protecting these reactive groups arewell known to those skilled in the art and numerous examples areillustrated herein. Another method involves addition of the substituentgroup after the crown compound is formed. Typical methods ofsynthesizing similar substituted crown compounds are described in FrenchPat. 1,440,716 and British Pat. 1,149,229 both to Charles John Pedersen.

In accordance with Formula I, the crown compounds are assemblages ofthree characteristic structural units; i.e., hetero atoms, alkylenegroups, and bivalent carbocyclic rings. The hetero atoms are divalentoxygen (O-) and trivalent nitrogen (ale) denoted by in Formula I. Thebivalent alkylene groups are 1,2-dimethylene (i.e. ethylene) and1,3-trimethylene, which are denoted by R in Formula I. Bivalentcarbocyclic ring residues or radicals are denoted by f the crowncompound and the chemical procedure used to prepare the crown compound.For instance, because oxy- 3 2 gen is divalent, no substituents on anoxygen atom in the macrocyclic ring are possible; both valenciesbeingutilized in forming the ring. Likewise, with two valencies of nitrogenutilized in forming a macrocyclic ring, the third valence can beoccupied by hydrogen or by substituents known in the art to be suitablefor replacement of hydro: gen on a secondary amine.

Included among suitable substituents on nitrogen are such groups asalkyl groups, aryl groups, alkaryl groups, acyl groups, nitroso groups,etc. Examples of these groups include: for alkyl; methyl, ethyl,n-propyl, isopropyl, alk-" oxyalkyl, and so forth up to about thevarious isomers of dodecyl; for aryl (including those carryingsubstituents), phenyl, tolyl, butyl phenyl, naphthyl, chlorophenyl,'nitro phenyl, carboxy phenyl, etc.; for alkaryl, benzyl, phenyl ethyl,naphthyl butyl, chlorobenzyl, etc.; for acyl groups (including in broadscope the residues obtained by removing halogen from an acyl halide)acetyl (its).

sulfonyl (-SO R), carbamoyl benzoyl etc., where R is an alkyl, aryletc.; and the (N=0).

Suitable substituents for the alkylene groups include nitroso groupalkyl, aryl, alkaryl and aralkyl groups, usch as those illustratedabove. As recognized in the art, condensation" reactions, which are usedto construct the macrocyclic ring system, proceed less satisfactorilywhen secondary or tertiary derivatives of the alkylene grou'pprecursors" (e.g. tosyl or chloro) are used. Side reactions interveneand yields are reduced. For this reason it is preferred" that a bivalentalkylene group carry only one substitu ent and not more than onesubstituent per carbon atom other than hydrogen.

Suitable substituents for the rings include halo, nitro,

nitroso, amino, azo, C -C alkyl, C -C alkenyl, C5-C aryl, (3 -0 aralkyl,(I -C cycloalkyl, c -c, a11 ox cyano, hydroxy, carboxy, sulfo, etc.

Additionally substituents can be a chain of carbon and hetero atoms asin the case where a nitrogen atom or atoms in a ring are attached toanother chain of carbon and hetero atoms such as a chain defined by thebracketed portion of Formula I. When this chain of carbon and bon andhetero atoms is connected at the separate ends; of the chain to twonitrogen atoms in difierent macrocyclic 2: rings, a bridged or clamcompound is formed. These compounds are illustrated by the followingformulae:

where R, W, a, b, x and are defined as above and Z is a bifunctionalorganic radical, such as alkylene, a chain of carbon and hetero atoms asdefined by the bracketed portion of Formula I, or a {-WRi group asdefined above;

wherein R, W, Y

i s at. 2 R o sponding aliphatic groups in which one or more of the (CHgroups'is replaced by (CH The term .ring atom refers to an atom in thechain, as;

)s-6 2( L I .L of a macrocyclic ring unless specifically used withreference to another ring, such as a carbocyclic ring.

Representative structures of the compounds of this invention are asfollows:

an "18 Crown,"

@I 3 "14 Crown,"

anj

o U 1 I (VII) /O NH a Lantern" Compound,

@ Q 0 O O N -(CH2)XN (VIII) a Clam Compound,

:3 15 Crown" D' O NH a 15 Crown" (XII) The symbol refers to an ethylenegroup {CH CH -L refers to a trimethylene group %CH CH CH and refers too-phenylene. The notation refers to o-cyclohexylene. The abovecompounds, IV, V, VI, VII, and XI contain 18, 22, 24, 14 and 15 carbonand hetero-atoms in the macrocyclic rings and are referred to herein as18 Crown, 22 Crown, 24 Crown," 14 Crown, and 15 Crown, respectively,based on the number of atoms in the macrocyclic rings. Compound IXcontains 22 atoms in bicyclic rings and is referred to as a Lanterncompound and compound X contains 36 atoms in two macrocyclic ringsconnected by a polymethylene bridge and is referred to as a Clamcompound. Numerous variations of these configurations will be apparentto those skilled in the art from these examples. Macrocyclic Crown,Lantern, and Clam compounds of this invention can be prepared withvarying number and sequence of carbon, hetero-atoms, and carbocyclicrings.

To promote complexing, hetero atoms in the macrocyclic ring should beseparated by links of no more than 3 ring-carbon atoms or no less than2-ring carbon atoms. Optimally, the ring hetero atoms are separated fromadjoining ring hetero atoms by 2 ring carbon atoms, e.g., -CH CHMacrocyclic imines having from 14-30 ring atoms will contain from 4 to10 hetero atoms, at least one hetero atom being nitrogen. Crowns can bemade in which all hetero atoms are nitrogen, but for general utility ascomplexing agents and with cost of preparation as a consideration apreferred group of imine crowns are those with at least two nitrogensand at least two oxygen atoms in the macrocyclic ring.

Carbocyclic nuclei or rings which are vicinally fused to a macrocyclicring in the imine crowns are selected from the group consisting ofmonocyclic and polycyclic aromatic hydrocarbons of the benzo seriesconsisting of from .1 to 3 fused rings (benzene, naphthalene,anthracene,

phenanthrene), and the perhydro analogues thereof. The nuclei can berepresented as R-substituted, i.e.

where R is hydrogen, halo, nitro, nitroso, amino, azo, C1-C4 alkyl,alkenyl, G g-C12 aryl, C7016 aralkyl, C -C alkoxy, cyano, hydroxy,carboxy, suite and the like and can be attached to any of the fouravailable ring positions. Provided the substituent group is stable withthe reactants employed in forming the novel imine crowns of theinvention, the group can be present in the vicinally difunctionalcompounds which are preferred starting materials for the formation ofthe crown compounds. In other instances the substituent can beintroduced after formation of the macrocyclic ring by conventionalchemical reaction, e.g., by azo coupling of an amino compound tointroduce the 2120 grouping. In yet other instances, the substituentscan be formed by chemical reaction of other substitueuts, e.g., nitrogroups can be reduced to amino groups.

Generally, macrocyclic ring compounds can be made by a series ofconsecutive and alternative condensation reactions. The particularsequence of reactions is patterned to produce the compound of thedesired size and configuration. Numerous examples of these reactions andparticular sequences are given herein.

A general synthesis procedure for the nitrogen crowns consists of aseries of stepwise condensations wherein aliphatic (or cycloaliphatic)tosylates or aliphatic halides react with amines (having one availableH-atom) or phenols or, less preferably, with alcohols. If desired,thiophenols or mercaptans may also be employed. The arrangement ofhetero atoms in the crown to be made will determine the sequence ofcondensation reactions chosen. Representative sequences are illustratedherein. In all cases, undesired side reactions are minimized byemploying protective groups to inactivate sites which can compete withthe desired ones; with reactants having N-atoms, beta to halo, or tosyl,e.g.

are preferably avoided. Representative protecting groups for amino andhydroxyl are benzyl, tetrahydropyranyl, methoxymethyl, trityl, andtert-butyl carbobenzoxy. References giving other protecting groups aregiven herein, infra.

The condensations are run in inert solvents, preferably boiling in therange IUD-160 C. Aromatic hydrocarbons, e.g. xylene, glyrnes, andalcohols are representative classes. The choice of reactants may bearupon the choice of solvents; thus, alcohols are not used as solvents andreactants at the same time.

Imino crowns in which a nitrogen is next to a carbocyclic ring aresynthesized from o-amino phenol, o-phenylene diamine or their saturatedanalogues using one of the following condensations as the primary step:

B 111E N-R RX nx on -on wherein B is a protective group and RX is analkyl halide or tosylate. RX can be a compound which would form a crownin one step, such as Br OH:

Imino crowns in which a nitrogen is present in a position other thannext to a carbocyclic ring can be synthesized from intermediates such asthose shown below or other suitably protected compounds:

O NH

NH I where B is defined as above. The same general conditions asdescribed above apply. Those skilled in the art will be able to deviseschemes for syntheses of a variety of imino crowns by judiciousprotection of hydroxyl and amino groups coupled with stepwisecondensations.

Crown compounds containing at least one carbocyclic fused nucleus orring (e.g. benzo group) can be built up from reactants having abenzenoid nucleus on which hydroxy or amino groups are independently,vicinally positioned (e.g. catechol, o-aminophenol,1,2-phenylenediamine). If a crown having a single carbocyclic fusednucleus is desired, a bridging group is built up from one of the vicinalgroups and joined to the other vicinal group, or a complete bridginggroup is attached first to one vicinal group and then to the other. If acrown having two carbocyclic fused nuclei is desired, there are severalgeneral methods. In one procedure, a bridging group is attached to (orbuilt up from) one vicinal group on a benzenoid nucleus; then two ofthese compounds are codimerized, each compound supplying one bridginggroup which joins the free vicinal group of the other to form themacrocyclic ring. In an alternative procedure, a pair of benzenoidnuclei are bridged; then the ends of a bridging group are attached tothe free vicinal groups (one on each nucleus) to form the macrocyclicring. If a crown having more than two carbocylic fused nuclei isdesired,

9 v the needed benzenoid nuclei are bridged in a linear manner to give apolymer having terminal benzenoid nuclei bearing one free vicinal groupapiece; a bridging group is then attached to these free vicinal groupsto form the macrocyclic ring.

Illustrative details will be given below and it will be evident to thoseskilled in the art that the number and position of the ring nitrogenatoms will influence the selection of a procedure for a specificcompound. It will be further evident that classical organic chemicalprocedures may have to be employed on occasion to protect one or morefunctional groups present, e.g. one of a pair of vicinal amino or one ofa pair of vicinal hydroxyl groups. Procedures for protecting functionalgroups are well summarized in Advances in Organic Chemistry, vol. III,Interscience Publishers, New York, 1963, pp. 159-294.

At one or more stages in the synthesis of the macrocyclic imines of thepresent invention a chain-lengthening reaction may be required. Thereaction of ethylene oxide with a compound (R') containing a hydroxyl orNH group will add \CH CH 1 O TH where "=1, 2, The analogous reaction ofoxacyclobutane will add Nitrogen atoms can be introduced by converting ahydroxyl group to the tosylate (Ts),

and cleaving the benzyl group by hydrogenating (H with palladium oncarbon catalyst (Pd/C) at 70 C. and 300 p.s.i.g., e.g.

Before cleavage the benzylamino-terminated intermediate can be furtherreacted with to add CH -CH OH and one of the above reactions can berepeated. The terminal hydroxyl group can be converted to its tosylateto allow introduction of a second benzylamine group; thus, chains of{-NHCH CH groups can be added. Alternatively, the terminal hydroxylgroup can be reacted with an oxide as in the first reaction above togive a link such as CH -CH O. If 3- chloropropanol is used in place ofethylene chlorohydrin, -(-NHCH CH CH groups result from thetosylate/benzylamine sequence. The spacing between heteroatoms can thusbe arranged by selecting the proper ether and the proper alcohol eachtime the chain is lengthened.

To obtain a fused c'arbocyclic ring joined to two nitrogen atoms, e.g.

a crown compound can be prepared from a 1,2-diamine, e.g.,1,2-phenylenediamine. It is convenient to block (protect) one of theamino groups by reacting it with carbo-tbutyloxy chloride, such aswidely used in peptide synthesis, to get the following intermediate:

-NHB

where B=carbo-t-butyloxy, can react with ditosylate ofN-benzyldiethanolamine,

NHB

to give ENH- When the carbo-t-butyloxy groups have been selectivelyremoved as described above, the liberated ring NH groups are ready forreaction with another molecule of the same ditosylate to form The benzylgroups can be removed by hydrogenating as indicated above.

In another variation,

(XIV) N-crn-om III-CHz-CH: H

Subsequently liberated amine groups can be reacted with a differentC1-CH CH -O terminated bridging compound such as (ClCHaCH: O z i) 2NCH2@to complete the ring, e.g.

following sequences illustrate how o-nitro-N-methylaniline is employed:

12 This intermediate is codimerized (in solution using xylene solventwith tat-amine to neutralize sulfonic acid byproduct and heating toreflux) to yield:

The benzyl groups can be cleaved if desired to give NH and the desiredcrown is recovered from by-product by well-known methods.

To obtain a carbocyclic fused ring attached to both N and O, e.g.

O-C;CaN-, o-aminophenol is a preferred starting compound. During thereaction the appropriate groups should be blocked.

Reaction of o-aminophenol with a bridging compound such asbis(;8-chloroethyl) ether,

gives an intermediate, e.'g.

which can be inter and intramolecularly cyclized to the ring compounds,

7. H o x i q and 0 In place of co-dimerization, the intermediate can bereacted with more o-arninophenol to give the bridged bisphenol OH H0 Theremaining bridge is completed by reaction with bis (5 chloroethyl) etherin the presence of base to yield:

13-v It is evident that a great variety of ethereal dichlorides can besubstituted for bis(B-chloroethyl) ether, e.g.

O CHQCHi Cl O CHaCH: C].

To obtain a carboxylic fused ring attached only to ysmr OCOC:O-,

cate'chol is a preferred starting compound. The hydroxyl groups cansimultaneously take part. in bridge building steps by the generalmethods stated above. For example,

The first three steps of this reaction XVI can be repeated to addadditional groups, e.g.

CH3 CH: l l NH-crn 1 NH-CHg-i O N N 3H, L6H

| t. (I J derived from 1,2-cycl0hexylene glycol, is substituted in thecyclization step of reaction XVII, one of the fused carboxylic ringswill be saturated,

the other will be aromatic l e.g.

The reactants are maintained at a low concentration (about 0.02 M orless) for the cyclization step to avoid polymerization of the reactants.

A one-step cyclization can occur when cyclohexane ditosylate is reactedwith a glycol having a blocked amino group in the presence of apotassium salt (e.g. potassium tert.-butylate) followed 'by treatmentwith dilute acid to remove trityl, e.g. v

OTs

(XVIII) A molar portion of the glycol and a 2-molar portion of base areseparately and simultaneously added to a molar portion of the ditosylatein tetrahydrofuran (TI-IF). After the reaction, the desired crowncompound is recovered from lay-products by known methods.

To attach one or more ethyleneoxy groups to a benzenoid nucleus havingvicinal hydroxyl groups, e.g.

The carbobenzyloxy group is removed when desired by catalytichydrogenation (Pd/C). Dihydropyran, benzyl, or alphachloromethyl methylether (in the presence of strong base) are alternative blocking agents;the phenolic hydroxyl group is regenerated by treatment with acid or byhydrogenation in the case of benzyl.

1,2-dihydroxylbenzene, such as catechol, can also be reacted withB-haloether groups in the presence of base to attach a bridging element,e.-g.

This process is described and illustrated in the aforementioned patentsto Charles John Pedersen, i.e. French Pat. 1,440,716 and British Pat.1,149,229. It is on the other hand, not desirable to use fi-haloaminocompounds, i.e.,

. 16 i l V where the halogen atom atom by two carbon atoms.

Macrocyclic imines having saturated fused carbocyclic groups can be madeby hydrogenating the corresponding macrocycles having fused benzenoidgroups. As indicated above, they can also be made by bridging vicinallydisubstituted saturated carbocyclic compounds, e.g., 1,2-cyclohexyleneglycol or 1,2-cyclohexylene-diamine, using cyclic ethers, tosylchloride, and benzylamine by the methods illustrated above for theiraromatic counterparts.

Due to the trifunctionality of nitrogen the crown compounds of thisinvention can contain macrocyclic rings fused via a pair of N-atoms in abicyclic structure (e.g. compound 1X). The bicyclic structure can beconsidered two nitrogen atoms connected by three chains of carbon andhetero-atoms. These bicyclic compounds are termed Lantern compounds. Thepresent invention includes bicyclic crowns where at least one fusedcarbocyclic substituent is present. Each heterocyclic ring preferablyhas at least 18 atoms. These compounds can have ring N- atoms other thanthe pair common to the fused heterocyclic rings; ring oxygen atoms canalso be present. Adjacent hetero atoms in the rings are separated by 2or 3 carbon atoms. Obviously each of the heterocyclic rings can have thesame sequence and number of atoms or each can be difierent in either orboth respects.

When only two N-atoms are present, the lantern compound can be made byreacting a diimino crown with nbutyl lithium and then reacting theresulting dilithio salt with a diprimary dihalide or ditosylate. Lanterncompounds containing fused aromatic carboxylic rings can be prepared byreacting a crown compound having aromatic carboxylic rings and two NH-groups in approximately opposed positions in the macrocyclic ring with aditosylate having a fused aromatic carboxylic ring in the presence ofBuLi, e.g.,

A representative reaction sequence is given in Eiiarnple 6, infra.Alternatively, an acylation reaction can be used, e.g.

is separated from a m'trogen The reaction is conducted at high dilutionand reduction of the acyl groups completes the synthesis.

Crown compounds having one unsubstituted ring N- atom can be bridged bya divalent group containing alkylene groups and hetero atoms to formclam compounds (e.g. see compound X, supra). The n-butyl lithiumreaction can be used to produce the clam compound. This process consistsessentially of reacting an imino crown compound with n-butyl lithium toproduce a dilithio salt, then reacting the dilithio salt with a compoundselected from the group of diprimary dihalide and ditosylate to producea clam compound, and recovering the clam compound. This novel process isa general procedure for alkylating an imine group which cannot bealkylated by previously known methods. The general process consistsessentially of reacting the imine with n-butyl lithium to produce alithio salt, then reacting the lithio salt with a compound selected fromthe group of primary alkyl halide and primary alkyl tosylate to producethe alkylated imine, and recovering the alkylated imine.

Other ring N-atoms can be present in the crown compounds than those tobe connected or bridged; protective groups can be used to shield theseN-atoms during the synthesis. The connecting chain or bridging group canbe an alkylene radical, wherein, optionally, one or more chain C-atomsare replaced by hetero atoms such as O, N, or S or by an arylene groupsuch as phenylene. The bridge in the clam compound can range from 1 to20 atoms in length or it can be longer. A preferred class of clamcompounds has a bridge which is derived from a polymer having amolecular weight up to about 5000. Numerous combinations for bridgingchains will be apparent from this disclosure to those skilled in theart. The bridge can be a chain of carbon and hetero atoms such asdefined by the bracketed portion of Formula I. Preferably no two heteroatoms in the bridge are adjacent and the total number of carbon andhetero atoms ranges from 1 to about 40. A preferred class of clamcompounds has a carbon/ hetero atom bridge which is substantially analkylene bridge, i.e., the majority of the bridge atoms are carbonatoms.

The bridging process can be done by reacting an imino crown having a--NH- group with an appropriate difunctional reactant. Example 5illustrates conversion of an imino crown to its Li salt with n-butyl Liand the reaction of that salt with an w-alkylene diprimary dihalide toform a clam as a di-tertiary amine. Direct reaction of an imino crownwith a diacyl halide, e.g. adipoyl chloride forms a clam as a ditertiaryamide; phosgene forms a clam as a urea (thiophosgene will give thethiourea). The bridge may be built in situ by reacting alkylene oxides,e.g. ethylene and propylene oxide, with an imino crown. Direct reactionof an imino crown with a diisocyanate gives a clam as a urea; typicaldiisocyanates are 1,6-hexamethylene diisocyanate,2,4-toluenediisocyanate, and the reaction product of an excess of2,4toluenediisocyanate with poly(propyleneether) glycol.

The crown product can be isolated and recovered by conventional methodssuch as by concentration of the reaction mixture or by mechanicalcollection of insoluble (or precipitated) product. The crown compoundsare freed from impurities, such as straight-chain reactants byrecrystallization from organic liquids such as alcohol, chloro form,ethanol, benzene and heptane.

Carbocyclic nuclei or rings fused in the macrocyclic ring can be eitheraromatic or saturated. In general, complexes formed with saturated crowncompounds are more soluble and stable in aliphatic solvents than arethose formed with aromatic crown compounds. On the other hand, presencein the crown compound of aromatic nuclei carries with it certainadvantages. For example, complex formation with aromatic crowns can befollowed by commercial ultra-violet spectrophotometers. The fullysaturated crown compounds do not absorb within the limits of suchinstruments. By appropriate choice of reactants or by partiallyhydrogenating aromatic crown compounds, so as to obtain compounds havingboth aromatic and saturated nuclei fused thereto, compounds having theadvantages of each type can be prepared.

Various methods of incorporating saturated carbocyclic nuclei in thecrown compounds will be apparent to those skilled in the art from thisdisclosure. For example, 1,2-diaminocyclohexane can be reacted directlywith the dihalide reactant to produce a macrocyclic ring havingcyclohexane fused to it. Again, saturated compounds like 1,2-bis(fi-chloroethoxy)cyclohexane can be reacted with an amino di-terminatedopen chain reactant to yield a saturated imine crown.

Aromatic crowns can be fully or partially saturated by catalytichydrogenation. The temperature of hydrogenation is suitably from 60 toC. Pressures can range from 500 to 2000 p.s.i.g. Typical times requiredare from 3 to 20 hours. It will be realized, however, that these valuesare not critical. Some cleavage of the macrocyclic ring occurs, leadingto the formation of by-products in addition to the desired hydrogenationproduct. These prod ucts can be separated and the desired hydrogenationprod uct can be isolated by conventional physical methods, such asfractional crystallization and the like from solvents} such as'alcohol,chloroform, 2-ethoxy-ethanol benzene and heptane, or by chromatographicseparation. If the desired product does not otherwise contain activehydrogen groups, the reaction product can be reacted with reagents suchas organic isocyanates, which react readily with hydroxy compounds, tofacilitate separation of the products.

The crown compounds described herein can be used to form a novel complexwith a compatible cation of a. metal compound. Particularly noteworthyare the complexes formed with ionic alkali metal compounds and alkalineearth metal compounds. The cation can be inorganic or organic.

The complex forming ability of crown compounds generally depends uponring size and the number of nitrogen and oxygen atoms in the compound.Complexing ability cannot be predicted with certainty prior to actuallytesting the cation or cations with various crown compounds. However,certain trends are noticeable. One is that the complexing ability for aseries of crown compounds of a given ring size is less for the alkaliand alkaline earth metal cations for the compounds having fewer oxygenatoms in the ring. The complex forming ability for a series of crowncompounds of a given ring size is greater for Ag+ with those compoundshaving more nitrogen atoms in the ring. Lantern compounds exhibitconsiderably stronger complexing ability for appropriate cations thanmonocyclic ring crowns of comparable ring size.

The complexes appear to be electrostatic in character rather thancoordination complexes for alkali and alkaline earth cations. A complexcan be formed with a cation selected from a group of cations havingvarious valences and sizes. In most crown complexes it is believed thatthe cation is located near the center of the macrocyclic ring. A complexcan have more than one ring per cation especially with large cations.Under some circumstances the complex can be solvated. The crowncompounds of this invention can form complexes with the cations Na+, K+,Ag Ba++, Sr- Ca++, Rb+ and probably others. Other cations, such as Li-Cs Cu+, Au NH RNH Hg' Hg' Tl+, Pb++, Ce+++ and the like form complexeswith similar crown compounds.

In complexes of alkali metal compounds and the like, substituents on themacrocyclic imine ring as described herein do not greatly aflect theformation of the crown complexes. However, substituents do influenceconsiderably some other properties of the complexes, particularly thesolubility. In general the saturated crown compounds form complexeswhich are more soluble in most common solvents than complexes formedwith the corresponding aromatic compound. In some instances, thecomplexes are more soluble in organic solvents than the crown compoundsthemselves.

Imine groups and substituents on the macrocyclic ring afiect the abilityto convert the crown compound and complex to other compounds and theability to attach other compounds to the crown compound and complex.

Complexes of the macrocyclic imines with compounds of alkali metals oralkaline earth metals can be prepared by a variety of methods.Crystalline complexes can be prepared by dissolving the crown compoundand a cation source in a suitable solvent which is later removed byevaporation from the resulting complex, usually under vacuum.Alternatively, complexes can be prepared by dissolving crown compoundand metal compound in a minimum quantity of hot solvent which dissolveseach, the resulting complex being precipitated by cooling andmechanically separated, e.g., by filtration, centrifugation, etc. Again,crown compound can be heated with metal compound in a solvent in whichonly the latter is readily soluble, the crown compound being convertedinto a crystalline complex without the system even becoming a clearsolution. The complex is then recovered by filtration. Other methods ofcomplex formation Will occur to the art-skilled in light of the above.

In general, selected complexes prepared according to this invention cansolubilize complexed metal compounds in media wherein they are normallyinsoluble. This property alone suggests manifold applications of theinvention in industry. For example, the benzene-soluble potassiumhydroxide complex can be employed to initiate the anionic polymerizationof acrylonitrile or pivalolactone, a hydroxyl-terminated polymer productresulting. It can also be used as a soluble acid-acceptor in nonproticsystems.

The crown compounds are useful for the separation of dissolved salts.The salt which can form a crown complex can thereafter be extracted byan immiscible solvent .which cannot dissolve the uncomplexed saltspresent. By way of illustration, water-soluble salts that form crownedcomplexes can be separated from salts that do not; a water-insolublesolvent for the complex is employed for the extraction. For example,2,3-(4'-methylbenzo) 1,4 diamino-7,10,13,16 tetraoxacylooctadeca- 2-enedoes not complex with magnesium ion; hence, silver salts can 'beseparated from magnesium salts by this method.

The crown compounds of the invention can also be used as dyeintermediates by adding an active hydrogencontaining substituent, e.g.OH-, amino, etc. to the aromatic nucleus by conventional techniques andthereafter coupling the compound with a diazo compound according towell-known methods.

The following examples are illustrative of compounds of the invention.Parts, proportions, and percentages are by weight unless otherwisestated.

EXAMPLE 1 (A) Preparation of2,3-benzo-1-aza-4,7,10,13-tetraoxacyclopentadeca-Z-ene or1-aZa-2,3-benzo-15 crown-5 which has the following formula isaccomplished as follows:

o-Aminophenol (17.1 grams, 0.157 gram-moi), 1,11-dichloro-3,6,9-trioxaundecane (36.6 grams, 0.157 grammol), and 250milliliters of n-butanol at 25 C. are added to a one-liter, round-bottomglass flask equipped with a thermometer, a water-cooled refluxcondenser, and an agitator and continually maintained under a protectivenitrogen atmosphere. After the resulting mixture has been refluxed,while agitated, at a pot temperature of 121 C. for 18 hours, it iscooled to 67 C. A solution of 12.6 grams (0.315 gram-mol) of sodiumhydroxide in 12 milliliters of water is added. Then the resultingmixture is refluxed, while agitated, at a pot temperature of 101 C. for10 hours.

The crown compound is isolated as follows: The warm reaction massobtained above is filtered and the filtrate is freed from volatiles byheating in a steam heated rotary vacuum evaporator at C. and 0.2 mm. Hg.The residue, about 42 grams of brown viscous oil, is dissolved in 200ml. of chloroform. The solution is twice washed with 100 ml. of 5%aqueous sodium hydroxide; it is dried over 20 grams of anhydrousmagnesium sulfate, filtered, and concentrated in a rotary vacuumevaporator at 100 C. and 0.2 mm. Hg. The residue, 35.2 grams of brownviscous oil, is distilled in a steam heated rotary vacuum evaporator at100 C. and 0.2 mm. Hg. The distillate, about 10.3 grams of liquid, issolidified into white crystals which is2,3-benzo-1-aza-4,7,10,13-tetraoxacyclopentadeca-Z-ene or1-aza-2,3-benzo-15 crown-5. Recrystalization of the crown compound fromn-heptane produces shiny white crystals melting at 100-101 C.

Infrared spectra (IR) show a sharp infrared band at 2.98 microns besidesthe broad ether bands. The nuclear magnetic resonance (NMR) spectrum isconsistent with the indicated structure. NMR is a standard method ofstructure determination. It is described in detail in Applications ofNuclear Magnetic Resonance Spectroscopy in Organic Chemistry by Jackmanand Sternhill, Pergamon Press, New York, 2nd ed., 1969, and NuclearMagnetic Resonance A pplication to Organic Chemistry by Roberts,McGraw-Hill Book Company, New York, 1959. Analysis yields the followingdata:

Analyti- Caled for Analysis cal CnHmNOa C, percent 62.5, 62.7 62.9 H,pereent 7.9, 7. 9 7. 9 N, percent--." 5. 1 5. 2 Molecular wt 272 267Analyti- Calcd for Analysis cal CuHzmNzOs 0, percent 56.8, 56.9 56.7 H,percent 6.6, 6.7 6.8 N, percent 9. 4 9. 5

Analyti- Caled for Analysis cal CuHzoNzOa 0, percent... 59.1, 59.4 56.7

H, percent.-. 7.0, 7.2 6.8

N, pereent..-.. 7. 3 9. 5

EXAMPLE 2 Preparation of2,3-benzo-l-aza-4,7,l0,13,16-pentaoxacyclooctadeca-Z-ene represented bythe following formula is accomplished according to the followingprocedure:

o-Aminophenol (20.7 grams, 0.19 gram-mol),1,14-dichloro-3,6,8,12-tetraoxatetradecane (52.2 grams, 0.19 gram-mol),and 250 ml. of n-butanol at 25 C. are charged into the reactor andrefluxed therein under nitrogen with good agitation for seven hours at apot temperature of 121 C. Cooling is then applied to lower thetemperature to 70 C. A solution of 15.3 grams (0.383 grammol) of sodiumhydroxide in 16 ml. of water is added and the resulting mixture isrefluxed for 15 hours at a pot temperature of l10l C.

The warm reaction mixture is filtered. The filtrate is freed fromvolatiles by heating in a steam heated rotary evaporator at 100 C. andabout 0.2 mm. Hg. The residue, 60.9 grams of viscous dark brown oil, isextracted with 400 ml. of n-heptane. Concentration of the heptanesolution gives 12.6 grams of an orange liquid which is distilled in asteam heated rotary vacuum evaporator at 0.2 mm. Hg. The distillate, 9.3grams of pale yellow oil, is the desired2,3-benzo-1-aza-4,7,l0,13,16-pentaoxacyclooctadeca-Z-ene, which uponpurification yields the following analysis:

22 EXAMPLE 3 (A) Preparation of 5,6,14,15-dibenzo-4,7,10,13,16-pentaoxa-l-azacyclooctadeca-S,14-diene represented by the followingformula is accomplished by the following procedure:

H /0 I l 0 A 3-liter round-bottom glass flask, equipped with a stirrer,condenser, and additional funnel, is charged with 78 grams (0.027gram-mol) of bis[2-(0-hydroxyphenoxy)ethyl]ether, 1700 ml. of n-butanol,and a solution of 33.0 grams (0.84 gram-mol) of sodium hydroxide in ml.of water. The agitated mixture is heated to reflux; 50 grams (0.27gram-mol) of 2,2'-dichloro-diethylamine hydrochloride are added. Theresulting mixture is refluxed for two days, then cooled and filtered.Concentration by vacuum distillation of the filtrate yields a solidresidue which is dissolved in hot benzene and filtered. Evaporation ofthe benzene gives 5,6,l4,l5-dibenzo-4,7, 10,13,16-pentaoxa 1aza-cyclooctadeca-S,l4-diene. Recrystallization from dioxane gives a 22%theoretical yield. A sample of this product, after recrystallizationfrom toluene, melts at 152-153 C. and has the following analysis whichindicates the above formula:

Its NMR spectrum is consistent with the above formula.

(B) Preparation of N-ethyl derivative of5,6,14,15-dibenzo-4,7,10,13,16-pentaoxa 1 azacyclooctadeca 5,l4- dieneis accomplished by the following procedure: A 30- cc. stainless steelcylinder is charged with one gram (0.003 gram-mol) of5,6,l4,l5-dibenzo-4,7,l0,l3,l6- pentaoxa-l-azacyclooctadeca-S,14-diene,15 ml. of benzene, 0.24 ml. of ethyl iodide, and 1.5 ml. (0.003 grammol)of 2N aqueous sodium hydroxide. The cylinder is then sealed, kept at 100C. for 16 hours, cooled, and opened. The benzene layer inside thecylinder is separated from the aqueous caustic layer, boiled in thepresence of a gram or so of Darco decolorizing charcoal, and filteredhot. White crystals of the N-ethyl derivative of the crown compoundprecipitate having a melting point of -132 C. and the followinganalysis:

(C) Preparation of N-octyl derivative of 5,6,14,15-dibenzo 4,7,10,13,16pentaoxa-l-azacyclooctadeca-5,14- diene is accomplished by the followingprocedure: An oven dried, 500-ml. round-bottom glass flask equipped witha dry condenser, addition funnel, and stirrer is charged, successively,with 6.3 ml. (0.01 gram-mol) of a 15% solution of n-butyl lithium inhexane (commercially available from Foote Chemical), 20 ml. of thedimethyl ether of diethylene glycol, and a solution of 3.6 grams (0.01grammol) of5,6,l4,l5-dibenzo-4,7,10,13,16-pentaoxa-1-azacyclooctadeca-5,l4-diene inthe dimethyl ether of diethylene glycol. This mixture is heated to 110C. and kept at 110 C. for 2 hours; a solution of 2 grams (0.01 grammol)of n-octyl bromide m1. of anhydrous dimethyl ether of diethylene glycolis slowly added. The resulting mixture is then refluxed for 16 hours. Oncooling, solids 23 precipitate. These are removed by filtration afteraddition of 20 ml. of methanol. The filtrate is evaporated to drynessyielding the crude N-octyl derivative. This product is eluted from aneutral Woelm alumina column with benzene to produce several fractionswhich are combined and concentrated. Recrystallization of the resultingresidue from ethanol gives 1.6 grams (34% theoretical yield) of theN-octyl derivative of 5,6,l4,l5-dibenzo-4,7,l0,13,l6- pentaoxa 1azacyclooctadeca-S,14-diene. This product melts at 109-110" C. and hasthe following analysis:

Analyti- Calod for Analysis cal CnHnNOs 0, percent 71.5, 71. 8 71. 3 H,percent 8. 6, 8. 7 8. 6 N, percent 2. 9, 2. 9 2. 9

Nuclear magnetic resonance (NMR) analysis yields the following valueswhich are consistent with the structure shown: tau (3.1, s), tau (5.85,m), tau (6.75, t), tau (7.35, t), tan (8.65, s).

(D) N-acetyl derivative of 5,6,14,15-di'benzo-4,7,l0,13,-l6-pentaoxa-l-azacyclooctadeca-S,14-diene is prepared according to thefollowing procedure: A 250-ml. roundbottom glass flask equipped with anagitator, thermometer, and condenser is charged with 100 ml. of toluene,one gram (0.002 gram-mol) of 5,6,14,15-dibenzo-4,7,10,13,16-pentaoxa-l-azacyclooctadeca-5,14-diene, 0.2 ml. (0.004 gram-moi) ofpyridine, and 0.2 ml. (0.004 gram-moi) of acetyl chloride. The mixtureis refluxed for 1.5 hours, then cooled and diluted with 50 ml. of water.The organic and aqueous layers are separated, and the organic layerconcentrated to give the N-acetyl derivative of 5,6,14,15-dibenzo4,7,10,13,16-pentaoxa-l-azacyclooctadeca-S,14-diene. After this producthas been recrystallized from benzene, it produces white crystals havinga melting point of 198 C. and the following analysis:

Analytical Calcd for Analysis C22H21N u C, percent 66. 1 65.8 H,percent- 7. 1 6. 7 N, percent. 3. 4 3.

benzene is accomplished by the following procedure: A 2- literround-bottom glass flask equipped with a stirrer, condenser, andthermometer is charged with 104 ml. (1.3 gram-moi) of pyridine and 32.6grams (0.16 gram-mol) of o-bis[2-(hydroxy)etl1oxy] benzene, the0,0'-bis[2-hy droxyethyl] derivative of catechol. This agitated mixtureis cooled to 0 C. and 68 grams (0.35 gram-mol) of ptoluene sulfonylchloride are added at such a rate that the temperature does not exceedC. Agitation is continued for 3 more hours. A chilled solution of 210ml. of concentrated hydrochloric acid in 470 ml. of Water is addeddropwise to the flask. Solid ditosylate,0-bis[2-(ptoluenesulfonyl)ethoxyJbenzene is filtered off and air dried.It melts at 95-96 C. NMR is consistent with structure.

(B) Preparation of o-bis[2-(N-benzylamino)ethoxy]- benzene isaccomplished by the following procedure: A 10.7 gram (0.10 gram-mol)portion of benzylamine is added to a solution of 5 grams (0.01 gram-mol)of the ditosylate prepared according to the above procedure in 100 ml.of xylene. The resulting mixture is agitated at reflux for 16 hours; itis cooled to precipitate as undesired white fibrous by-product which isfiltered olf. Concentration of the filtrate under vacuum gives nearlypure o-bis[2-(N-benzylamino)ethoxy]benzene. The diamine can be usedwithout further purification.

(C) Preparation of the N,N-dibenzyl derivative of 5,6,14,15 dibenzo4,7,13,16-tetraoxa-1,10-diazacyclooctadeca-5,l4-diene represented by thefollowing formula is accomplished by the following procedure:

An 8-gram (0.02 gram-mol) sample of the diamine, prepared according tothe above procedure, 200 ml. of xylene, 10.2 grams (0.02 gram-mol) of0-=bis{2-(p-toluene sulfonyl)ethoxy] benzene, and 5.7 grams (0.04gram-mol) of tri-n-propylamine are agitated at reflux for 16 hours in a500-cc. round-bottom glass flask. The reaction mixture is subsequentlycooled; the solution is decanted from a tarry residue and concentratedby evaporation of the xylene to yield crude product. Boiling methanol isused to extract the impurities from it which leaves the undissolvedN,N-dibenzyl derivative of 5,6,l4,l5-dibenzo-4,7,- 13,l6-tetraoxa-1,10-diazacyclooctadeca-S,14-diene, having a melting pointof 176 C. and the following NMR spectrum which is consistent with thestructure; NMR: tau (2.7, m), tau (3.2, s), tau (5.9, t), tan (6.2, s),tau (6.85, t). This compound is used without further purification.

(D) Preparation of5,6,14,15-dibenzo-4,7,l3,16-tetraoxa-l,l0-diazacyclooctadeca-5,l4-dienerepresented by the following formula is accomplished by the followingprocedure:

A 4-gram sample of N,N-dibenzyl derivative of 5,6,14,- 15 dibenzo4,7,13,16-tetraoxa-l,lO-diazacyclooctadeca- 5,14-diene prepared as aboveis dissolved in 300 ml. of tetrahydrofuran. One gram ofpalladium-on-charcoal catalyst is added; the mixture is hydrogenated at50 C. and p.s.i.g. for 6 hours. Solids are removed from thehydrogenation mixture by filtration; the tetrahydrofuran is evaporated.The crude residue is purified by refluxing with methanol to dissolve thecrown compound. The product is obtained by evaporating the methanol andrecrystallizing from toluene to give 2.1 grams (80% theoretical yield)of5,6,14,15-dibenzo-4J,13,16-tetraoxa-1,IO-diazacycloocta-deca-S,14-dieneas white crystals melting at 176 C. and having the following analysis:

NMR: tau (3.15, s), tau (5.9, t), tau (6.9, t), tan (7.55, s).

The product is evaluated for ion complexing properties by forming asolution of a salt such as potassium chloride or silver nitrate. Thepotassium salt is conveniently ionized in methanol and the silver saltis conveniently ionized in Water. Under ambient conditions, solutions of5,6,14,15- dibenzo 4,7,13,16-tetraoxa-1,10-diazacyclooctadeca-5,14-diene, in the same solvent as the salt, are added to the salt solutions.Complexes with the metal ions form upon addition of the crown compounds.The degree ofcomplex formation is determined by potentiometricmeasurement of the salt solutions before and after the additions ofcrown compounds, using the apparatus and calculation methods describedin detail in Frensdorif Journal of the American Chemical Society, 93,600 (1971), Stability Constants of Cyclic Polyether Complexes WithUnivalent Cations. The silver complex of the crown compound of thepresent example is found to exhibit an equilibrium constant in water ofabout 10' liters/mole. This is significantly higher than the equilibriumconstant of about 10 liters/mole found for silver complexes of similarcrown compounds without nitrogen ring components. The potassium complexof the present crown compound exhibits an equilibrium constant of about10 liters/mole in methanol, while the equilibrium constant of potassiumcomplexes of similar crown compounds without nitrogen ring components isabout 10 liters/mole. Magnesium ion complexes much less readily thansilver with the crown compounds, similarly permitting separation of amixture of such ions.

The metal complexes of the crown compound can be isolated by evaporationor by crystallization from a concentrated solution. The crown complexescan then be separated from undesirable salts by dissolving the crowncomplex in an organic solvent such as chloroform, in which an inorganicsalt would not be soluble.

EXAMPLE 5 Preparation of N,N-decamethylenebis[5,6,14,15-dibenzo4,7,10,13,16 pentaoxa 1 azacyclooctadeca- 5,14-diene] represented by thefollowing formula is accomplished by the following procedure:

A dry 250-ml. round-bottom 3-neck glass flask equipped with a stirrer,condenser, and addition funnel, is charged under nitrogen with 100 ml.of anhydrous dimethyl ether of diethylene glycol and 1.8 grams (0.005gram-mol) of 5,6,14,15 dibenzo 4,7,10,13,16-pentaoxa 1azacyclooctadeca-5,14-diene. The mixture is heated and when the crowncompound has dissolved, 3 m1. (0.005 gram-mol) of a 15% solution ofn-butyl lithium in hexane is added. After the resulting mixture beginsto reflux, a solution of 0.75 gram (0.0025 gram-mol) of1,10-dibromodecane in ml. of the dimethyl ether of diethylene glycol isadded dropwise. The reaction mixture is refluxed and agitated for 16hours.

The reactor is then cooled to room temperature. Twentyfive millilitersof methanol are introduced to use up any unreacted n-butyl lithium; themixture is filtered; evaporation of solvents from the filtrate gives aresidue which is dissolved in chloroform, filtered, and concentrated.The residue is dissolved in chloroform and chromatographed on a basicWoelm column. The chloroform fractions contain crystals which melt at122124 C. after recrystallization. Recrystallization from tolueneproduces crystals which exhibit NMR spectra consistent with the expectedstructure of the clam compound N,N'-decamethylenebis [5,14,15 dibenzo4,7,10,13,16 pentaoxa 1 azacyclooctadeca-5,14-diene] and having thefollowing analysis:

A 0.0001 molar solution of the clam compound is prepared in ethanol. Themetal ions Na+ and Cs+ are added to the clam-ethanol solutions as salts.Ultraviolet spectra of these solutions indicate that a small amount ofthe Na+ is complexed by the clam compound but none of the Cs+.

EXAMPLE 6 Lantern Compound Preparation of5,6,14,15,22,23-t1ibenzo'4,7,13,16,21,24- hexaoxa 1,10 diazabicyclo[8.8.8] hexacosa-5,14,22- triene represented by the followingformula is accomplished by the following procedure.

/A/ f l LNL/ A dry 2-1iter round-bottom glass flask, equipped with astirrer, condenser, and addition funnel, is charged with 3.58 grams(0.01 gram-mol) of crown compound 5,6,14, 15 dibenzo 4,7,13,16 tetraoxa1,10 diazacyclooctadeca-5,14-diene (prepared according to the procedureof Part (D) of Example 4) and one liter of the anhydrous dimethyl etherof diethylene glycol under a nitrogen blanket. The mixture is heateduntil the crown compound dissolves. Then 12.5 ml. of a 15% solution of nbutyl lithium in hexane are added. The mixture is heated to reflux and5.1 grams (0.01 gram-mol) of the ditosylate ofbis-[2-o-(hydroxyphenoxy)ethyl]ether are slowly in troduced from theaddition funnel. Refluxing is continued for two days.

After the mixture has been cooled, a 5 ml. aliquot of methanol is added.The resulting composition is filtered and the filtrate concentrated in arotary vacuum evaporator. The brown viscous material which remains isadded to about 30 ml. of chloroform. The resulting solution is extractedwith water, dried, and concentrated to yield another viscous liquid.This residue is chromatographed on a basic Woelm alumina column (75 ml.capacity) using chloroform as solvent. The first two fractions elutedcontain a small amount of starting material and other components. Thesefractions are combined and rechromatographed on another basic Woelmcolumn, eluting with benzene. The yellow oil obtained on concentratingthe eluates is boiled in about 400 ml. of hexane. The resulting hexanesolution is decanted and concentrated to a 50-ml. volume; white crystalsof the lantern com-pound precipitate and are collected by filtration.The lantern compound melts at 108-1 13 C. and exhibits an NMR spectrum.consistent with the proposed structure and has the following analysis:

The products, of :Example 16 are tested vfor ion com- References Citedplexing ability in the manner described in Example 4(D) UNITED STATESPATENTS above. Using a potassium chloride salt in methanol the complexconstant of the present lantern compound with 3,580,889 5/ 1971 Barneyet a1 250340-3 potassium ion is about 10 This particularly highcomplexing ability makes the present compound especially use- 5 DONALDDAUS Pnmary Exammer ful in eifecting reactions with potassium in mediain which I, H, TURNIPSEED, A i t t E i potassium would not be readilysoluble.

We claim: o

1. 5,6,14,15 dibenzo 4,7,13,16 'tetraoxa 1,10 di- 10 260239 B, 333azacyclooctadeca-S,l4-diene.

US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO.3,847,949 0 DATED November 12, 1974 INVENTOR(S) Charles John Pedersenand Marilyn H. Bromels It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 1, line 24, the following amendment should be inserted: I

"Reference to Prior Application 0 This application is acontinuation-in-part of U. S. application Serial No. 36,689 filed May12,

1970, now abandoned." I 0 I Signed and Scaled this Tenth a A [SEAL] D yof ugust 1976 Q Arrest:

RUTH C. LIA SON C. MARSHALL DANN Anestmg Offrcer Commissioner of Parentsand Trademarks O

1. 5,6,14,15 - DIBENZO - 4,7,13,16 - TETRAOXA - 1,10 -DIAZACYCLOOCTADECA-5,14-DIENE.